Nu-(alpha-etherified-acetyl) carbamic acid esters



" Patented May28, 1946 N- (a-ETHERIFIED-ACETYL) CA RBAMIC ACID ESTERS Lowell B. Kilgore and Karl H.

Weber, Washington, D. C., assignors to Kilgore Development Corporation, Washington, D. (3., a corporation of Virginia No Drawing. Application March 5, 1945,

Serial No. 581,170

28 Claims. '(Cl.167-22) The invention described herein relates to new anic compounds, more particularly to a new class or N-substituted carbamic acid esters and specifically to N-(a-etherified-acetyl) carbamic acid esters.

An object of the present invention is to provide new and useful compounds of the general formula:

n o-jcnzco-aimcooa' wherein It represents a radical selected from the group consisting of alkyl, aryl, aralkyl, cyclo- The more detailed practice of the invention is illustrated by the following examples which, however, do not limit the scope of the invention in any way.

EXAMPLE 1 PREIARATION or BUrYL N-IBU'roxYAcnrYL .CARBAMATE 130 grams of thionyl chloride were added to 132 grams (one mol) of butoxyacetic acid dissolved in 100cc. of dry benzene. After refluxing untilreaction wa complete, the benzene alkyl and heterocyclic radicals and R represents a' radical selected from the group consisting of alkyl, aryl, aralkyhcycloalkyl and hetero-- cyclic radicals and; radicals of the type R"O'X- wherein x is alkylene and R" is.

a hydrocarbon group. A further object of this invention is the provision of a process for the preparation of these N(c-etherified-acetyl) carbamic acid esters. Still a further object of this invention is thepreparation of new chemicals suitable for combating insects. Other objects and advantages of this invention will appear hereinafter. These objects are accomplished by the followingv invention wherein N-(u-etherified-acetyl) carbamic acid esters are prepared by reacting the acyl halide of an c-etherifled acetic acid with' an ester of carbamic acid as follows. ROCH2COCI+H2NCOOR' ROCHzCONHzCOORJ-i-HCI R and R radicals.

The esters of carbamic acid which are used as starting materials may be madeby any one of may be the ame or different organic several known methods; fo example, by heating urea with the appropriate alcohol (Organic Syntheses, Coll, vol. I, pp. 140-141) or by an exchange reaction in which'urethane is refluxed with a high boiling alcohol. Similarly the acyl halides of the c-etherified acetic acids employed in this invention ner; 7

The new compounds of this invention are ob tained by heating together a carbamic" acid ester and the acyl halide oi? an a-ether'ified acetic acid may be prepared in known manover varying periods of time depending on the reactivities of the individual components of the Where necessary a suitable reaction mixture. inert diluent such as benzene or toluene may be used. To facilitate the removal of HCl suitable organic bases such as pyridine, piperidine and the like may be added to the reaction mixture.

mixture refluxed for two days. product was, diluted with benzene, washed twice g with saturated sodium bicarbonate solution and After fractional distillationand excess thionyl chloride were distilled oil.

The butoxyacetyl chloride obtained in this manner was diluted with benzene. 120 grams of butyl carbamate were added and the reaction mixture was refluxed for twodays after which time evolution of HCl gas had ceased. The resulting-mix ture was washed with water, neutralized. with a solution of NaHCOs and again washed with water. The washed benzene solution was then fractionally distilled under reduced pressure. 142 grams of product boiling at -20/2mm.

was obtained.

EXAMPLE 2 PREPARATION or Isosm N-BUTOXYACETYL CARBAMATE Butoxyacetyl chloride was prepared b refluxing 32 grams of butoxyacetic acid with 30 grams of thionyl chloride in 25 cc. dry benzene until reaction was complete. The solvent and excess thionyl chloride were distilled oil. 32 grams of isoamyl carbamate and 25 cc. dry benzene were added to the butoxyacetyl chloride and the twice with water. under reduced pressure, 30 grams of isoamyl N-butoxyacetylcarbamate boiling at 132-6f/2mm. were obtained. I

n EXAMPLE 3 PREPARATION or PROPYL N-OCTOXYACETAL CARBAMATE Octoxyacetyl chloride was prepared by refluxing 13.2 grams of octoxyacetic acid with 8.4 grams of thionyl chloride in benzene. -Excess thionyl chloride was distilled off together with some solvent and 7.2 grams of prop'yl carbamate was added. The mixture was refluxed for 18 hours, washed with water, then saturated sodium'bicarbonate solution. water again and then The reaction solution, water again, and then distilled.

' thionyl .chloride dissolved in benzene.

thionyl chloride was distilled off with some $01-' OCTYL N-Tsrasnrnxomr'uaox'rscam (Imam-rs Tetrahydrofurfuroxyacetyl chloride was pre pared by refluxing 12 grams of tetrahydrofurfur- PREPARATION or senative members of this new series of organic compounds against the common house fly. The

- test procedure used was the sandwich bait oxyacetic acid with 9 grams of thionyl chloride dissolved in benzene. Excess thionyl chloride was distilled or! together with some solvent and 12.5 grams of n-octyl carbamate was added. The mixture was refluxed for 12 /2 hours, washed with water, then saturated sodium bicarbonate 16 grams of product boiling at 152-'72/lmm. were obtained. EXAMPLE 5 Pasraa'rron or E'IHYL N-Pnans'moxvacs'rrr.

CARBAM'ATE Phenethoxyacetyl chloride was prepared by refluxing 12.6 grams of phenethoxyacetic acid with 8.4 grams of thionyl chloride dissolved in benzene. Excess thionyl chloride was distilled ofi with some solvent and 6.2 grams of ethyl carbamate was added. The mixture was refluxed for 16 hours. After washing as in previous examples, the mixture was distilled under reduced pressure. '7 grams of product boiling at 170-5/1mm. were obtained.

EXANIPLE 6 PREPARATION or B-Ernoxxnrnrr. N-Bu'roxrscam Cansamrs Butoxyacetyl chloride was prepared by refluxmg 13.2 grams of butoxyacetic acid with 12 grams Excess method substantially as described in Soap, June, 1939, page 103. A coating otmolasses was applied to one side of a strip of blotting P per and dried to a hard, glossy surface. It was covered with a strip of thin, porous tissue which had previously been immersed in a 4 percent solution in alcohol of the compound to be-tested and then dried until the alcohol had evaporated. The concentration of the test solutions was reduced to 4 percent because the repellency of certain. members of the series was so prolonged that the flies were in danger of dying before completion of the test. For comparison purposes one strip was treated onlywith solvent. The strips prepared in this fashion were mounted on a board and invent and 13.3 grams of B-ethoxyethylcarbamate was added. The mixture was refluxed for 17 /2 hours; After washing as in previous examples the mixture was distilled under reduced pressure.

8 grams of product boiling at. 1'15-7/l8mm. were.

obtained.

Other members of the new series of N-uetherifled-acetyl carbamic acid esters which we have prepared by the method set out in the aforedescribed examples are:

Cyclohexyl N-butyoxyacetyl carbamate Tetrahydrofuriuryl N-butoxyacetyi carbamate Phenethyl N-butoxyacetyl carbamate Butyl N-B-naphthoxyacetyl carbamate Amyl N-phenoxyacetyl carbamate Phenethyl N-p chlorophenoxyacetyl carbamate' Dodecyl N-cyclohexoxyacetyl carbamate lsoamyl N-cyclohexoxyacetyl carbamate Dodecyl N-ethoxyac'etyl carbamate Butyl N -2,3,4,6 tetrachlorophenoxyacetyl carbamate I Butyl N-lauroxyacetyl carbamate Phenyl butoxyacetyl carbamate B-ethoxyethyl N-butomcetyl carbamate B-butox'yethyl N-butoxyac'etyl carbamate B-phenoxyethyi N-phenoxyacetyl carbamate B-benzowethyi N-cyclohexoiwacetyl' carbamate The new N-(a-etherifled-acetyl) carbamic acid esters as a class possess valuable insect combatand mosquitoes.

Table 1 demonstrates the efiectiveness of repretroduced into a large cage containing more than 2000 hungry houseflies. By making readings at intervals, the duration of repellency, namely, the time which elapsed before the flies began to feed on the molasses'through the treated tissue covers was observed. 1

Table I [Duration of repeilency to houseflies possessed by N-(a-etherliledacetyl) carbamic'scid esters in 4 percent concentrationJ 1 Bait still untouched at end oi this period. Test terminated to EXAMPLE '1 Butyl N-butoxyacetyl carbamate, when applied to the forearm of an individual, retained its repellency to Aedes aeyilpti mosquitoes for. 202 minutes.

It has. beenobserved, furthermore, that the compounds of the present invention possess a lethal action when applied to houseilies in the form of a spray. They are particularly eflective as paralytic agents. I

The various N-(a-etherifled-acetyl) carbamic acid esters may be used direct. Eflective lotions may also be prepared by dissolving these compounds in alcohol. Other diluents may also be used such as aqueous alcohol, isopropanol and diinethyl phthalate. These new compounds may also be dissolved in hydrocarbon oils such as kerosene, in which form they are particularly useful .as cattle sprays.

Although this invention has been described with reference to preferred illustrative embodiments thereof it will be apparent to those skilled in the art that the principles 01' this invention may be embodied in other forms but within the scope oi. the appended claims.

What we claim is:

1. The N-(d-etherifled-acetyl) carbamic acid esters having the general formula:

aocmoonncooa' wherein R represents a radical selected from the group consisting of albl, aryl, aralkyl. cycloalkyl an heterocyclic radicals; and R represents e rs cal selected iron the group consisting oi allwi,

eral formula:

' having the general formula:

wherein alk is alkyl and R represents a. radical selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and heterocyclic radicals and radicals of the type R"-O-X'- wherein X is alkylene and R" is a hydrocarbon group.

3. The N-butoxyacetyl carbamic acid esters having the general formula C4H9OCH2CONHCOOR wherein R represents a radical selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and heterocyclic radicals and radicals of the type R"O-X wherein X is alkylene and R" is a hydrocarbon group.

4. Butyl N-butoxyacetyl carbamate.

5. Isoamyl N-butoxyacetyl carbamate.

6. Propyl N-octoxyacetyl carbamate.

7. The process of preparing N-(a-etherifledacetyl) carbamic acid esters which comprises reacting the acyl halide of an a-etherifled acetic acid with a carbamic acid ester. I

8. The process of preparing N-butoxyaoetyl carbamic acid esters which comprises reacting the acyl halide of butoxyacetic acid with a carbamic acid ester.

9. An insect combative composition containing as an essential active ingredient an N-(a-etherified-acetyl) carbamic acid ester having the gen- ROCHzCONI-ICOOR' wherein R. represents a radical selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl, and heterocyclic radicals; and R represents a radical selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and heterocyclic radicals and radicals of the type R"--OX wherein X is alkylene and R" is a hydrocarbon group.

10. An insect combative composition containing-a N-(a-etherified-acetyl) carbamic acid ester having the general formula:

ROCHaC'ONI-ICOOR .wherein elk is-alkyl and R represents a. radical selected from the group consisting of alkyl, aryl,

aralkyl, cycloalkyl and'heterocyclic radicals and radicals of the type R."-X- wherein X is alkylene and R" is a hydrocarbon group.

12. An insect combative composition containing as an essential active ingredient an N-alkoxyacetyl carbamic acid ester having the-general formula:

- Alk-O CHzCONHCOOR' wherein alk isalkyl and R represents a radical selected from the group consisting of alkyl, aryl,

aralkyl, cycloalkyl and heterocyclic radicals and radicals of. the type R"-OX- wherein X is alkylene and R" is a hydrocarbon group and a carrier therefor;-

13. An insect combative composition containing as an essential active ingredient an N-butoxyacetyl carbamic acid ester having the general for- 'mula:

cimocnlcomroooa' wherein R represents a radical selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and heterocyclic radicals and radicals of the type R"-O--X-- wherein X is alkylene and R" is a hydrocarbon group. i

14. An insect combative composition contain ing an N -butoxyacetyl carbamic acid ester havin the general formula:

C4H9OCH2CONHCOOR' wherein R represents a radical selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and heterocyclic radicals and radicals of the .ing as an essential active ingredient butyl N- butoxyacetyl. carbamate.

16. An insect combative composition containrier therefor.

1'7. .An insect combative composition containing as an essential active ingredient isoamyl N-butoxyacetyl carbamate.

18. An insect combative composition containing isoamyl'N-butoxyacetyl carbamate and a carrier therefor.

19. An insect combative composition containing as an essential active ingredient propyl N-octoxyacetyl carbamate.

20. An insect'combative composition containing propyl N-octomacetyl carbamate and a carrier therefor. I

21. An insect combative composition containing as an essential active ingredient an N-(ozetherified-acetyl) carbamic acid ester having the general formula: 1

ROCHaCONHCQOB' wherein R. represents a radical selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and heterocyclic radicals; and R represents a radical selected from .the group consisting of alkyl, aryl, arallwl, cycloalkylend heterocyclic radicals and radicals of the type Rf'-O-X- wherein X is alkylene and R" is a hydrocarbon group dissolved in aqueous alcohol.

I 22. An insect combative composition containing as an essential active ingredient an N-(aetheritled-acetyl) carbamic acid ester having the eneral formula: v

ROCHaCONHCOOR' wherein R represents a radical selected from the ing the general, formula:

ROCH=CONHCOOR' wherein R represents a radical selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl and heterocyclic radicals; and R represents a m-o-cmcoNHcooR' wherein all: is alkyl and R represents a radical selected from the group consisting of alkyl. aryi, aralkyl, cycloalkyl and heterocyclic radical and radicals of the type R"O--X- wherein X is alkylene and R." is ahydrocarbon group.

25. The process of combating insects which comprises subjecting them to the action of an N-butoxyacetyl carbamic acid ester having the general formula: Y

cintocmcomrcoom wherein R represents a radical selected from the group consisting of alkyl. aryl, aralkyl, cycloalkyl and'heterocyclic radicals and radicalsof the typeR"--OX wherein X is a hydrocarbon group.

26. The process of combating insects which comprises subjecting them to the action oi butyl N-butoxyacetyl carbamate'.

2'1. The process of combating'insects which comprises subjecting them to the action of isoamyl N-butom'acetyl carbamate.

2B. The process of combating insects which comprises subjecting them to the action of propyl N-octoxyacetyl carbamate. 7

LOWELL B. moan. KARL H. mm. 

